Method for preparing polypropylene using transition metal compound containing thiophene-fused cyclopentadienyl ligand

ABSTRACT

The present invention relates to a preparation method for polypropylene that comprises polymerizing a propylene monomer in the presence of a catalyst comprising a novel transition metal compound. Using the novel transition metal compound as a catalyst, the preparation method for polypropylene according to the present invention can not only acquire high catalytic activity for polymerization to achieve high efficiency of the process but allow it to easily control the fine-structure characteristics of the polymer, thereby providing polypropylene having desired properties with ease.

FIELD OF THE INVENTION

The present invention relates to a method for preparing a polypropylene using a transition metal compound containing a thiophene-fused cyclopentadienyl ligand.

BACKGROUND OF THE INVENTION

Depending on the stereo-structure, polypropylene is classified into isotactic polypropylene (hereinafter, referred to as “iPP”), syndiotactic polypropylene (hereinafter, referred to as “sPP”), and atactic polypropylene (hereinafter, referred to as “aPP”).

Relative to the iPP and sPP which have good mechanical properties and thermal characteristics and thus have been actively exploited, the aPP is still undeveloped in terms of commercial use due to its low isotacticity and consequent limitation in enhancement of properties.

The aPP can be isolated as a by-product during the recovery of an aliphatic solvent in the slurry process for preparation of iPP, or prepared in the presence of a heterogeneous catalyst containing a modified titanium (III) chloride and an organoaluminum compound, such as diethyl aluminum chloride, as a co-catalyst or an activator. However, the iPP process with improved isotacticity cannot yield an amorphous aPP as a by-product but needs the addition of a co-monomer even when a PP with low crystallinity is produced according to the use purpose.

There has recently been a suggestion to a method for preparing an aPP with narrow molecular weight distribution using a variety of metallocene catalyst systems. The metallocene catalyst systems useful in this method are, for example, (a) an achiral, unbridged metallocene or stereo-rigid C2v symmetric metallocene catalyst, (b) meso-isomeric ansa metallocene catalyst, (c) an ansa-C2 symmetric metallocene catalyst with a bridge at 2,2′-position of the indenyl ring, and (d) a catalyst of monoCp compound.

The properties of the aPP greatly change according to the molecular weight of the aPP. For example, the aPP with a weight average molecular weight below 15,000 is sticky at the room temperature and thus has a limitation in its use, consequently with low applicability as a polymer material.

Further, the conventional metallocene catalyst systems have a low catalytic activity for polymerization to prepare a polypropylene and require a relatively low polymerization temperature (for example, 20° C. or below) enough to acquire an aPP with high molecular weight.

DISCLOSURE OF INVENTION Technical Problem

It is therefore an object of the present invention to provide a method for preparing a polypropylene using a catalyst having high catalytic activity and providing an aPP with high molecular weight.

Technical Solution

To achieve the object of the present invention, there is provided a method for preparing a polypropylene that comprises polymerizing a propylene monomer in the presence of a catalyst comprising a transition metal compound represented by the following formula 1:

In the formula 1, M is a Group 4 transition metal;

Q¹ and Q² are independently a halogen, C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl, C₆-C₂₀ aryl, C₁-C₂₀ alkyl C₆-C₂₀ aryl, C₆-C₂₀ aryl C₁-C₂₀ alkyl, C₁-C₂₀ alkylamido, C₆-C₂₀ arylamido, or C₁-C₂₀ alkylidene;

R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, and R¹⁰ are independently hydrogen; C₁-C₂₀ alkyl with or without an acetal, ketal, or ether group; C₂-C₂₀ alkenyl with or without an acetal, ketal, or ether group; C₁-C₂₀ alkyl C₆-C₂₀ aryl with or without an acetal, ketal, or ether group; C₆-C₂₀ aryl C₁-C₂₀ alkyl with or without an acetal, ketal, or ether group; or C₁-C₂₀ silyl with or without an acetal, ketal, or ether group, where R¹ and R² can be linked to each other to form a ring; R³ and R⁴ can be linked to each other to form a ring; and at least two of R⁵ to R¹⁰ can be linked to each other to form a ring; and

R¹¹, R¹², and R¹³ are independently hydrogen; C₁-C₂₀ alkyl with or without an acetal, ketal, or ether group; C₂-C₂₀ alkenyl with or without an acetal, ketal, or ether group; C₁-C₂₀ alkyl C₆-C₂₀ aryl with or without an acetal, ketal, or ether group; C₆-C₂₀ aryl C₁-C₂₀ alkyl with or without an acetal, ketal, or ether group; C₁-C₂₀ silyl with or without an acetal, ketal, or ether group; C₁-C₂₀ alkoxy; or C₆-C₂₀ aryloxy, where R¹¹ and R¹², or R¹² and R¹³ can be linked to each other to form a ring.

In the transition metal compound of the formula 1, M is titanium (Ti), zirconium (Zr), or hafnium (Hf); Q¹ and Q² are independently methyl or chlorine; R¹, R², R³, R⁴, and R⁵ are independently hydrogen or methyl; and R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², and R¹³ are independently hydrogen.

The catalyst may further comprise at least one co-catalyst compound selected from the group consisting of compounds represented by the following formula 6, 7, or 8.

—[Al(R⁶¹)—O]_(a)—  [Formula 6]

In the formula 6, R⁶¹ is independently a halogen radical, a C₁-C₂₀ hydrocarbyl radical, or a halogen-substituted C₁-C₂₀ hydrocarbyl radical; and a is an integer of 2 or above.

D(R⁷¹)₃  [Formula 7]

In the formula 7, D is aluminum (Al) or boron (B); and R⁷¹ is independently a halogen radical, a C₁-C₂₀ hydrocarbyl radical, or a halogen-substituted C₁-C₂₀ hydrocarbyl radical.

[L-H]⁺[Z(A)₄]⁻ or [L]⁺[Z(A)₄]⁻  [Formula 8]

In the formula 8, L is a neutral or cationic Lewis acid; Z is a Group 13 element; and A is independently a C₆-C₂₀ aryl or C₁-C₂₀ alkyl radical having at least one hydrogen atom substituted with a halogen radical, a C₁-C₂₀ hydrocarbyl radical, a C₁-C₂₀ alkoxy radical, or a C₆-C₂₀ aryloxy radical.

As for the co-catalyst compound, in the formula 6, R⁶¹ is methyl, ethyl, n-butyl, or isobutyl. In the formula 7, D is aluminum, and R⁷¹ is methyl or isobutyl; or D is boron, and R⁷¹ is pentafluorophenyl. In the formula 8, [L-H]⁺ is a dimethylanilinium cation, [Z(A)₄]⁻ is [B(C₆F₅)₄]⁻, and [L]⁺ is [(C₆H₅)₃C]⁺.

The content of the co-catalyst compound is given such that the molar ratio of a metal in the co-catalyst compound with respect to one mole of a transition metal in the transition metal compound of the formula 1 is 1:1 to 1:100,000.

Further, the catalyst may comprise the transition metal compound of the formula 1 bound to at least one support selected from the group consisting of SiO₂, Al₂O₃, MgO, MgCl₂, CaCl₂, ZrO₂, TiO₂, B₂O₃, CaO, ZnO, BaO, ThO₂, SiO₂—Al₂O₃, SiO₂—MgO, SiO₂—TiO₂, SiO₂—V₂O₅, SiO₂—CrO₂O₃, SiO₂—TiO₂—MgO, bauxite, zeolite, starch, and cyclodextrine.

The polymerization may be carried out under conditions of −50 to 500° C. and 1 to 3,000 atm.

The polypropylene may have a weight average molecular weight of 20,000 to 1,000,000; and a density of 0.8 to 0.9 g/ml.

Further, the polypropylene may have an isotacticity (Pentad I.I, mmmm) of 5 to 20%.

ADVANTAGEOUS EFFECTS

Using a novel transition metal compound as a catalyst, the preparation method for polypropylene according to the present invention can not only acquire high catalytic activity for polymerization to achieve high efficiency of the process but easily control the fine-structure characteristics of the polymer, thereby providing polypropylene having desired properties with ease.

DETAILED DESCRIPTION OF THE INVENTION

Hereinafter, a description will be given as to a method for preparing a polypropylene according to the embodiments of the present invention.

In the course of repeated studies on the catalysts for olefin polymerization, the inventors of the present invention have found out a novel ligand in which an amido ligand is linked to an ortho-phenylene ligand to form a condensed ring, and a 5-membered cyclic pi-ligand linked to the ortho-phenylene ligand is fused with a heterocyclic thiophene ligand. Also, they have found it out that a transition metal compound comprising the ligand exhibits higher catalytic activity and provides a polymer with higher molecular weight than a transition metal compound not fused with a heterocyclic thiophene ligand.

Particularly, it has been revealed that the use of the transition metal compound comprising the novel ligand in the preparation of polypropylene (preferably, aPP) makes it easier to control the fine-structure characteristics of the copolymer and thus allows the preparation of a polypropylene with high molecular weight, thereby completing the present invention.

In accordance with one embodiment of the present invention, there is provided a method for preparing a polypropylene that comprises polymerizing a propylene monomer in the presence of a catalyst comprising a transition metal compound represented by the following formula 1:

In the formula 1, M is a Group 4 transition metal;

Q¹ and Q² are independently a halogen, C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl, C₆-C₂₀ aryl, C₁-C₂₀ alkyl C₆-C₂₀ aryl, C₆-C₂₀ aryl C₁-C₂₀ alkyl, C₁-C₂₀ alkylamido, C₆-C₂₀ arylamido, or C₁-C₂₀ alkylidene;

R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, and R¹⁰ are independently hydrogen; C₁-C₂₀ alkyl with or without an acetal, ketal, or ether group; C₂-C₂₀ alkenyl with or without an acetal, ketal, or ether group; C₁-C₂₀ alkyl C₆-C₂₀ aryl with or without an acetal, ketal, or ether group; C₆-C₂₀ aryl C₁-C₂₀ alkyl with or without an acetal, ketal, or ether group; or C₁-C₂₀ silyl with or without an acetal, ketal, or ether group, where R¹ and R² can be linked to each other to form a ring; R³ and R⁴ can be linked to each other to form a ring; and at least two of R⁵ to R¹⁰ can be linked to each other to form a ring; and

R¹¹, R¹², and R¹³ are independently hydrogen; C₁-C₂₀ alkyl with or without an acetal, ketal, or ether group; C₂-C₂₀ alkenyl with or without an acetal, ketal, or ether group; C₁-C₂₀ alkyl C₆-C₂₀ aryl with or without an acetal, ketal, or ether group; C₆-C₂₀ aryl C₁-C₂₀ alkyl with or without an acetal, ketal, or ether group; C₁-C₂₀ silyl with or without an acetal, ketal, or ether group; C₁-C₂₀ alkoxy; or C₆-C₂₀ aryloxy, where R¹¹ and R¹², or R¹² and R¹³ can be linked to each other to form a ring.

Firstly, the catalyst used in the preparation method of the present invention will be described.

The catalyst comprises a transition metal compound represented by the formula 1.

The transition metal composition of the formula 1 is activated with an under-mentioned co-catalyst compound to provide catalytic activity for polymerization reaction of propylene.

The transition metal compound of the formula 1 comprises a novel ligand in which an amido ligand is linked to an ortho-phenylene ligand to form a condensed ring, and a 5-membered cyclic pi-ligand linked to the ortho-phenylene ligand is fused with a heterocyclic thiophene ligand. Accordingly, the transition metal compound exhibits higher catalytic activity for polymerization of propylene than the transition metal compound not fused with a heterocyclic thiophene ligand.

According to the present invention, in the compound of the formula 1, R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², and R¹³ are independently substituted with a substituent, including acetal, ketal, and ether groups. With such substituents, the transition metal compound can be more favored in being supported on the surface of a support.

In the compound of the formula 1, M is preferably titanium (Ti), zirconium (Zr), or hafnium (Hf).

Preferably, Q¹ and Q² are independently halogen or C₁-C₂₀ alkyl. More preferably, Q¹ and Q² are independently chlorine or methyl.

R¹, R², R³, R⁴, and R⁵ are independently hydrogen or C₁-C₂₀ alkyl, preferably hydrogen or methyl. More preferably, R¹, R², R³, R⁴, and R⁵ are independently hydrogen or methyl, with the provision that at least one of R³ and R⁴ is methyl; and R⁵ is methyl.

Preferably, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², and R¹³ are independently hydrogen.

The transition metal compound of the formula 1 preferably includes the above-mentioned substituents with a view to controlling the electronic and steric environments around the metal.

On the other hand, the transition metal compound of the formula 1 can be obtained from a precursor compound represented by the following formula 2:

In the formula 2, R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹² and R¹³ are as defined in the formula 1.

In this regard, the precursor compound of the formula 2 may be prepared by a method comprising: (a) reacting a tetrahydroquinoline derivative represented by the following formula 3 with alkyl lithium and adding carbon dioxide to prepare a compound represented by the following formula 4; and (b) reacting the compound of the formula 4 with alkyl lithium, adding a compound represented by the following formula 5, and then treating with an acid:

In the formulas 3, 4 and 5, R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹² and R¹³ are as defined in the formula 1.

In the formulas 3, 4 and 5, R¹, R², R³, R⁴, and R⁵ are independently hydrogen or C₁-C₂₀ alkyl, preferably hydrogen or methyl. More preferably, R′, R², R³, R⁴, and R⁵ are independently hydrogen or methyl, with the provision that at least one of R³ and R⁴ is methyl; and R⁵ is methyl. Preferably, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², and R¹³ are independently hydrogen. In this manner, the precursor compound is advantageous in securing easy accessibility and reactivity of a starting material and controlling the electronic and steric environments for the desired transition metal compound of the formula 1.

The step (a) involves reacting a tetrahydroquinoline derivative of the formula 3 with alkyl lithium and then adding carbon dioxide to form a compound of the formula 4, which process can be achieved by the methods disclosed in the known documents (Tetrahedron Lett. 1985, 26, 5935; Tetrahedron 1986, 42, 2571; and J. Chem. SC. Perkin Trans. 1989, 16).

In the step (b), the compound of the formula 4 is reacted with alkyl lithium to activate deprotonation and produce an ortho-lithium compound, which is then reacted with a compound of the formula 5 and treated with an acid to obtain a precursor for transition metal compound of the formula 2.

The method of producing an ortho-lithium compound by reaction between the compound of the formula 4 and alkyl lithium can be understood from known documents (Organometallics 2007, 27, 6685; and Korean Patent Registration No. 2008-0065868). In the present invention, the ortho-lithium compound is reacted with a compound of the formula 5 and treated with an acid to produce a precursor for transition metal compound of the formula 2.

The compound of the formula 5 can be prepared by a variety of known methods. For example, the following Scheme 1 can be used to prepare the precursor for the transition metal compound of the present invention with ease in a one-step process, which is economically beneficial by using inexpensive starting materials (J. Organomet. Chem., 2005, 690, 4213).

On the other hand, a variety of known methods can be employed to synthesize the transition metal compound of the formula 1 from the precursor for transition metal compound represented by the formula 2 obtained by the above-stated preparation method. According to one embodiment of the present invention, 2 equivalents of alkyl lithium is added to the precursor for transition metal compound of the formula 2 to induce deprotonation for producing a dilithium compound of cyclopentadienyl anion and amide anion, and (Q¹)(Q²)MCl₂ is then added to the dilithium compound to eliminate 2 equivalents of LiCl, thereby preparing the transition metal compound of the formula 1.

According to another embodiment of the present invention, the compound of the formula 2 is reacted with M(NMe₂)₄ to eliminate 2 equivalents of HNME₂ and produce a transition metal compound of the formula 1, where both Q¹ and Q² are NMe₂. The transition metal compound is then reacted with Me₃SiCl or Me₂SiCl₂ to replace the NMe₂ ligand with a chlorine ligand.

On the other hand, the catalyst used in the preparation method of the present invention may further comprise a co-catalyst compound.

The co-catalyst compound is to activate the transition metal compound of the formula 1. Thus, any kind of compound can be used as the co-catalyst compound without limitation in its construction, provided that it can activate the transition metal compound without deteriorating the catalytic activity of the catalyst of the present invention.

In accordance with one embodiment of the present invention, the co-catalyst compound is preferably at least one selected from the group consisting of compounds represented by the following formula 6, 7, or 8:

—[Al(R⁶¹)—O]_(a)—  [Formula 6]

In the formula 6, R⁶¹ is independently a halogen radical, a C₁-C₂₀ hydrocarbyl radical, or a halogen-substituted C₁-C₂₀ hydrocarbyl radical; and a is an integer of 2 or above.

D(R⁷¹)₃  [Formula 7]

In the formula 7, D is aluminum (Al) or boron (B); and R⁷¹ is independently a halogen radical, a C₁-C₂₀ hydrocarbyl radical, or a halogen-substituted C₁-C₂₀ hydrocarbyl radical.

[L-H]⁺[Z(A)₄]⁻ or [L]⁺[Z(A)₄]⁻  [Formula 8]

In the formula 8, L is a neutral or cationic Lewis acid; Z is a Group 13 element; and A is independently a C₆-C₂₀ aryl or C₁-C₂₀ alkyl radical having at least one hydrogen atom substituted with a halogen radical, a C₁-C₂₀ hydrocarbyl radical, a C₁-C₂₀ alkoxy radical, or a C₆-C₂₀ aryloxy radical.

In this regard, the co-catalyst compound of the formula 6 is not specifically limited in its construction, provided that it is alkylaluminoxane, and may be preferably methylaluminoxane, ethylaluminoxane, butylaluminoxane, hexylaluminoxane, octylaluminoxane, decylaluminoxane, etc.

Further, the co-catalyst compound represented by the formula 7 may be trialkylaluminum (e.g., trimethylaluminum, triethylaluminum, tributylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, etc.); dialkylaluminum alkoxide (e.g., dimethylaluminum methoxide, diethylaluminum methoxide, dibutylaluminum methoxide, etc.); dialkylaluminum halide (e.g., dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, etc.); alkylaluminum dialkoxide (e.g., methylaluminum dimethoxide, ethylaluminum dimethoxide, butylaluminum dimethoxide, etc.); alkylaluminum dihalide (e.g., methylaluminum dichloride, ethylaluminum dichloride, butylaluminum dichloride, etc.); trialkyl boron (e.g., trimethyl boron, triethyl boron, triisobutyl boron, tripropyl boron, tributyl boron, etc.); or tris-pentafluorophenyl boron.

Further, the co-catalyst compound represented by the formula 8 may be trimethylammonium tetrakis(pentafluorophenyl)borate, triethylammonium tetrakis(pentafluorophenyl)borate, tripropylammonium tetrakis(pentafluorophenyl)borate, tri(n-butyl)ammonium tetrakis(pentalluorophenyl)borate, tri(sec-butyl)ammonium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium n-butyl tris(pentafluorophenyl)borate, N,N-dimethylanilinium benzyl tris(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(4-(t-butyldimethylsilyl)-2,3,5,6-tetrafluorophenyl)borate, N,N-dimethylanilinium tetrakis(4-(t-triisopropylsilyl)-2,3,5,6-tetrafluorophenyl)borate, N,N-dimethylanilinium pentafluorophenoxy tris(pentafluorphenyl)borate, N,N-diethylanilinium tetrakis(pentafluorphenyl)borate, N,N-dimethyl-2,4,6-trimethylanilinium tetrakis(pentafluorophenyl)borate, N,N-dimethylammonium tetrakis(2,3,5,6-tetrafluorophenyl)borate, N,N-diethylammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate, tripropylammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate, tri(n-butyl)ammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate, dimethyl(t-butyl)ammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate, N,N-dimethylanilinium tetrakis(2,3,4,6-tetrafluorophenyl)borate, N,N-dimethyl-2,4,6-trimethylanilinium tetrakis(2,3,4,6-tetrafluorophenyl)borate, and so forth

Further, the co-catalyst compound of the formula 8 may also be dialkylammonium (e.g., di-(i-propyl)ammonium tetrakis(pentafluorophenyl)borate, dicyclohexylammonium tetrakis(pentafluorophenyl)borate, etc.); trialkylphosphonium (e.g., triphenylphosphonium tetrakis(pentafluorophenyl)borate, tri(o-tolylphosphonium tetrakis(pentafluorophenyl)borate, tri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl)borate, etc.); dialkyloxonium (e.g., diphenyloxonium tetrakis(pentafluorophenyl)borate, di(o-tolyl)oxonium tetrakis(pentafluororphenyl)borate, di(2,6-dimethylphenyloxonium tetrakis(pentafluorophenyl)borate, etc.); dialkylsulfonium (e.g., diphenylsulfonium tetrakis(pentafluorophenyl)borate, di(o-tolyl)sulfonium tetrakis(pentafluorophenyl)borate, bis(2,6-dimethylphenyl)sulfonium tetrakis(pentafluorophenyl)borate, etc.); or carbonium salts (e.g., tropylium tetrakis(pentafluorophenyl)borate, triphenylmethylcarbenium tetrakis(pentafluorophenyl)borate, benzene(diazonium)tetrakis(pentafluorophenyl)borate, etc.).

According to the present invention, in order for the co-catalyst compound to exhibit the enhanced effect of activation, the conditions are preferably given as follows: in the formula 6, R⁶¹ is methyl, ethyl, n-butyl, or isobutyl; in the formula 7, D is aluminum (Al), and R⁷¹ is methyl or isobutyl; or D is boron (B), and R⁷¹ is pentafluorophenyl; and in the formula 8, [L-H]⁺ is a dimethylanilinium cation, [Z(A)₄]⁻ is [B(C₆F₅)₄]⁻, and [L]⁺ is [(C₆H₅)₃C]⁺.

The added amount of the co-catalyst compound may be determined in consideration of the added amount of the transition metal compound of the formula 1, the required amount of the co-catalyst for sufficient activation of the transition metal compound, and so forth.

According to the present invention, the content of the co-catalyst compound is given such that the molar ratio of a metal in the co-catalyst compound with respect to one mole of a transition metal in the transition metal compound of the formula 1 is 1:1 to 1:100,000, preferably 1:1 to 1:10,000, more preferably 1:1 to 1:5,000.

More specifically, the co-catalyst of the formula 6 may be used at a molar ratio of 1:1 to 1:100,000, preferably 1:5 to 1:50,000, more preferably 1:10 to 1:20,000 with respect to the transition metal compound of the formula 1.

Further, the co-catalyst compound of the formula 7, where D is boron (B), may be used at a molar ratio of 1:1 to 1:100, preferably 1:1 to 1:10, more preferably 1:1 to 1:3, with respect to the transition metal compound of the formula 1.

Although dependent upon the amount of water in the polymerization system, the co-catalyst compound of the formula 7, where D is aluminum (Al), may be used at a molar ratio of 1:1 to 1:1,000, preferably 1:1 to 1:500, more preferably 1:1 to 1:100, with respect to the transition metal compound of the formula 1.

Further, the co-catalyst of the formula 8 may be contained at a molar ratio of 1:1 to 1:100, preferably 1:1 to 1:10, more preferably 1:1 to 1:4 with respect to the transition metal compound of the formula 1.

On the other hand, the catalyst used in the preparation method of the present invention may be a catalyst in which the transition metal compound of the formula 1 or a combination of the transition metal compound and the co-catalyst compound is bound to the surface of a support.

In this regard, the support as used herein may be any kind of inorganic or organic support used in the preparation of a catalyst in the prior art.

According to one embodiment of the present invention, the support may be SiO₂, Al₂O₃, MgO, MgCl₂, CaCl₂, ZrO₂, TiO₂, B₂O₃, CaO, ZnO, BaO, ThO₂, SiO₂—Al₂O₃, SiO₂—MgO, SiO₂—TiO₂, SiO₂—V₂O₅, SiO₂—CrO₂O₃, SiO₂—TiO₂—MgO, bauxite, zeolite, starch, cyclodextrine, or synthetic polymer.

Preferably, the support includes hydroxyl groups on its surface and may be at least one selected from the group consisting of silica, silica-alumina, and silica-magnesia.

The supporting method for the transition metal compound and the co-catalyst compound on a support may include: a method of directly supporting the transition metal compound on a dehydrated support; a method of pre-treating the support with the co-catalyst compound and then adding the transition metal compound; a method of supporting the transition metal compound on a support and then adding the co-catalyst compound for after-treatment of the support; or a method of reacting the transition metal compound and the co-catalyst compound and then adding the support.

In accordance with one embodiment of the present invention, the solvent as used in the supporting method is, for example, aliphatic hydrocarbon-based solvents (e.g., pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, etc.); aromatic hydrocarbon-based solvents (e.g., benzene, monochlorobenzene, dichlorobenzene, trichlorobenzene, toluene, etc.); halogenated aliphatic hydrocarbon-based solvents (e.g., dichloromethane, trichloromethane, dichloroethane, trichloroethane, etc.); or mixtures thereof.

In terms of the efficiency of the process for supporting the transition metal compound and the co-catalyst compound on a support, the supporting process may be preferably carried out at a temperature of −70 to 200° C., preferably −50 to 150° C., more preferably 0 to 100° C.

The preparation method for polypropylene according to the present invention may comprise polymerizing a propylene monomer in the presence of the afore-mentioned catalyst.

In this regard, the propylene monomer is not specifically limited and may include any kind of propylene generally used in the related art of the present invention.

Further, the polymerization step may be carried out by way of slurry, solution, gas, or bulk polymerization.

In the polymerization step conducted in the solution or slurry phase, the solvent or the olefin-based monomer itself can be used as a medium.

The solvent as used in the polymerization step may be aliphatic hydrocarbon solvents (e.g., butane, isobutane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, cyclopentane, methylcyclopentane, cyclohexane, etc.); aromatic hydrocarbon-based solvents (e.g., benzene, monochlorobenzene, dichlorobenzene, trichlorobenzene, toluene, xylene, chlorobenzene, etc.); halogenated aliphatic hydrocarbon solvents (e.g., dichloromethane, trichloromethane, chloroethane, dichloroethane, trichloroethane, 1,2-dichloroethane, etc.); or mixtures thereof.

In the polymerization step, the added amount of the catalyst is not specifically limited and may be determined within a range allowing a sufficient polymerization reaction of the monomer depending on whether the process is carried out by way of slurry, solution, gas, or bulk polymerization.

According to the present invention, the added amount of the catalyst is 10⁻⁸ to 1 mol/L, preferably 10⁻⁷ to 10⁻¹ mol/L, more preferably 10⁻⁷ to 10⁻² mol/L, based on the concentration of the central metal of the transition metal compound per unit volume (L) of the monomer.

Further, the polymerization step may be carried out by way of the batch type, semi-continuous type, or continuous type reaction.

The temperature and pressure conditions for the polymerization step are not specifically limited and may be determined in consideration of the efficiency of the polymerization reaction depending on the types of the reaction and the reactor used.

According to the present invention, the polymerization step may be carried out at a temperature of −50 to 500° C., preferably 0 to 400° C., more preferably 0 to 300° C. Further, the polymerization step may be carried out under the pressure of 1 to 3,000 atm, preferably 1 to 1,000 atm, more preferably 1 to 500 atm.

On the other hand, the preparation method for polypropylene according to the present invention allows it to control the fine-structure characteristics of the copolymer with ease by using the afore-mentioned catalyst, thereby providing a polypropylene with high molecular weight and low density.

In other words, the polypropylene may have a weight average molecular weight (Mw) of 20,000 to 1,000,000, preferably 50,000 to 900,000, more preferably 50,000 to 800,000.

The polypropylene may have a density of 0.8 to 0.9 g/ml, preferably 0.82 to 0.9 g/ml, more preferably 0.82 to 0.89 g/ml.

Further, the polypropylene may have an isotacticity (Pentad I.I, mmmm) of 5 to 20%, preferably 5 to 18%, more preferably 5 to 15%.

Further, the polypropylene may have a molecular weight distribution (Mw/Mn) of 1 to 10, preferably 1.5 to 8, more preferably 2 to 6.

On the other hand, the preparation method for copolymer according to the present invention may further comprise, in addition to the afore-mentioned steps, a step known to those skilled in the art before or after the afore-mentioned steps, which are not given to limit the preparation method of the present invention.

Hereinafter, a detailed description will be given as to the present invention in accordance with the preferred embodiments, which are given by way of illustration only and not intended to limit the scope of the present invention.

The following synthesis procedures (i) and (ii) for the precursor and the transition metal compound were performed in the atmosphere of inert gas, such as nitrogen or argon, according to the following Schemes 2 and 3, using the standard Schlenk and glove box techniques.

The individual compounds in the Scheme 2 come in different substituents. The substituents are presented in the table given below the corresponding compound (for example, the compound D-2 denotes a compound having a hydrogen atom for R^(a) and a methyl group for R^(b) and Ft^(c)).

In the Scheme 2, the compound C(C-1, C-2, or C-3) was synthesized by a known method (J. Organomet. Chem., 2005, 690, 4213).

(i) Synthesis of Precursor Example i-1 Synthesis of Precursor D-1

A Schlenk flask containing 1,2,3,4-tetrahydroquinoline (1.00 g, 7.51 mmol) and diethyl ether (16 ml) was cooled down in a cold bath at −78° C. and stirred while n-butyl lithium (3.0 mL, 7.5 mmol, 2.5 M hexane solution) was slowly added under the nitrogen atmosphere. After one-hour agitation at −78° C., the flask was gradually warmed up to the room temperature. A light yellowish solid precipitated, and the butane gas was removed through a bubbler. The flask was cooled down back to −78° C. and supplied with carbon dioxide. Upon injection of carbon dioxide, the slurry-type solution turned to a clear homogenous solution. After one-hour agitation at −78° C., the flask was gradually warmed up −20° C. while the extra carbon dioxide was removed through the bubbler to remain a white solid as a precipitate.

Tetrahydrofuran (0.60 g, 8.3 mmol) and t-butyl lithium (4.9 mL, 8.3 mmol, 1.7 M pentane solution) were sequentially added at −20° C. in the nitrogen atmosphere, and the flask was agitated for about 2 hours. Subsequently, a tetrahydrofuran solution (19 mL) containing lithium chloride and the compound C-1 (1.06 g, 6.38 mmol) was added in the nitrogen atmosphere. The flask was agitated at −20° C. for one hour and then gradually warmed up to the room temperature. After one-hour agitation at the room temperature, water (15 mL) was added to terminate the reaction. The solution was moved to a separatory funnel to extract the organic phase. The extracted organic phase was put in a separatory funnel, and then hydrochloric acid (2 N, 40 mL) was added. After shaking up the solution for about 2 minutes, an aqueous solution of sodium hydrocarbonate (60 mL) was slowly added to neutralize the solution. The organic phase was separated and removed of water with anhydrous magnesium sulfate to eliminate the solvent and yield a sticky product. The product thus obtained was purified by the silica gel column chromatography using a mixed solvent of hexane and ethylacetate (v/v, 50:1) to yield 77.2 mg of the desired compound (43% yield).

In the ¹H NMR spectrum of the final product, there was observed a set of two signals at ratio of 1:1, resulting from the difficulty of rotating about the carbon-carbon bond (marked as a thick line in the Scheme 2) between phenylene and cyclopentadiene. In the following ¹³C NMR spectrum, the values in parenthesis are chemical shift values split due to the difficulty of rotation.

¹H NMR (C₆D₆): δ 7.22 and 7.17 (br d, J=7.2 Hz, 1H), 6.88 (s, 2H), 6.93 (d, J=7.2 Hz, 1H), 6.73 (br t, J=7.2 Hz, 1H), 3.84 and 3.80 (s, 1H, NH), 3.09 and 2.98 (q, J=8.0 Hz, 1H, CHMe), 2.90-2.75 (br, 2H, CH₂), 2.65-2.55 (br, 2H, CH₂), 1.87 (s, 3H, CH₃), 1.70-1.50 (m, 2H, CH₂), 1.16 (d, J=8.0 Hz, 3H, CH₃) ppm.

¹³C NMR (C₆D₆): 151.64 (151.60), 147.74 (147.61), 146.68, 143.06, 132.60, 132.30, 129.85, 125.02, 121.85, 121.72, 119.74, 116.87, 45.86, 42.54, 28.39, 22.89, 16.32, 14.21 ppm.

Example i-2 Synthesis of Precursor D-2

The procedures were performed in the same manner as described in the synthesis of the compound D-1 in Example i-1, excepting that the compound C-2 was used rather than the compound C-1, to yield a precursor compound D-2. The yield was 53%.

In the ¹H NMR spectrum of the final product, there was observed a set of two signals at ratio of 1:1, resulting from the difficulty of rotating about the carbon-carbon bond (marked as a thick line in the Scheme 2) between phenylene and cyclopentadiene.

¹H NMR (C₆D₆): δ 7.23 (d, J=7.2 Hz, 1H), 6.93 (d, J=7.2 Hz, 1H), 6.74 (br t, J=7.2 Hz, 1H), 4.00 and 3.93 (s, 1H, NH), 3.05 (br q, J=8.0 Hz, 1H, CHMe), 3.00-2.80 (br, 2H, CH₂), 2.70-2.50 (br, 2H, CH₂), 2.16 (s, 3H, CH₃), 2.04 (br s, 3H, CH₃), 1.91 (s, 3H, CH₃), 1.75-1.50 (m, 2H, CH₂), 1.21 (d, J=8.0 Hz, 3H, CH₃) ppm.

¹³C NMR (C₆D₆): 151.60 (151.43), 145.56 (145.36), 143.08, 141.43, 132.90, 132.68, 132.43, 129.70, 121.63, 120.01, 116.77, 46.13, 42.58, 28.42, 22.97, 15.06, 14.19, 14.08, 12.70 ppm.

Example i-3 Synthesis of Precursor D-3

The procedures were performed in the same manner as described in the synthesis of the compound D-1 in Example i-1, excepting that tetrahydroquinaline was used rather than tetrahydroquinoline, to yield a precursor compound D-3. The yield was 63%.

In the ¹H NMR spectrum of the final product, a certain signal was split into a set of four signals at ratio of 1:1:1:1, resulting from the difficulty of rotating about the carbon-carbon bond (marked as a thick line in the Scheme 2) between phenylene and cyclopentadiene and isomerism pertaining to the existence of two chiral centers.

¹H NMR (C₆D₆): δ 7.33, 7.29, 7.22, and 7.17 (d, J=7.2 Hz, 1H), 6.97 (d, J=7.2 Hz, 1H), 6.88 (s, 2H), 6.80-6.70 (m, 1H), 3.93 and 3.86 (s, 1H, NH), 3.20-2.90 (m, 2H, NCHMe, CHMe), 2.90-2.50 (m, 2H, CH₂), 1.91, 1.89, and 1.86 (s, 3H, CH₃), 1.67-1.50 (m, 1H, CH₂), 1.50-1.33 (m, 1H, CH₂), 1.18, 1.16, and 1.14 (s, 3H, CH₃), 0.86, 0.85, and 0.80 (d, J=8.0 Hz, 3H, CH₃) ppm.

¹³C NMR (C₆D₆): 151.67, 147.68 (147.56, 147.38), 147.06 (146.83, 146.28, 146.10), 143.01 (142.88), 132.99 (132.59), 132.36 (131.92), 129.69, 125.26 (125.08, 124.92, 124.83), 122.03, 121.69 (121.60, 121.28), 119.74 (119.68, 119.46), 117.13 (117.07, 116.79, 116.72), 47.90 (47.73), 46.04 (45.85), 31.00 (30.92, 30.50), 28.00 (27.83, 27.64), 23.25 (23.00), 16.38 (16.30), 14.63 (14.52, 14.18) ppm.

Example i-4 Synthesis of Precursor D-4

The procedures were performed in the same manner as described in the synthesis of the compound D-1 in Example i-1, excepting that the compound C-2 and tetrahydroquinaline were used rather than the compound C-1 and tetrahydroquinoline, to yield a precursor compound D-4. The yield was 63%.

In the ¹HNMR spectrum of the final product, a certain signal was split into a set of four signals at ratio of 1:1:1:1, resulting from the difficulty of rotating about the carbon-carbon bond (marked as a thick line in the Scheme 2) between phenylene and cyclopentadiene and isomerism pertaining to the existence of two chiral centers.

¹H NMR (C₆D₆): δ 7.32, 7.30, 7.22, and 7.19 (d, J=7.2 Hz, 1H), 6.97 (d, J=7.2 Hz, 1H), 6.85-6.65 (m, 1H), 4.10-3.90 (s, 1H, NH), 3.30-2.85 (m, 2H, NCHMe, CHMe), 2.85-2.50 (m, 2H, CH₂), 2.15 (s, 3H, CH₃), 2.02 (s, 3H, CH₃), 1.94, 1.92, and 1.91 (s, 3H, CH₃), 1.65-1.50 (m, 1H, CH₂), 1.50-1.33 (m, 1H, CH₂), 1.22, 1.21, 1.20, and 1.19 (s, 3H, CH₃), 1.10-0.75 (m, 3H, CH₃) ppm.

¹³C NMR (C₆D₆): 151.67 (151.57), 145.58 (145.33, 145.20), 143.10 (143.00, 142.89), 141.62 (141.12), 134.08 (133.04), 132.84 (132.70, 136.60), 132.50 (132.08), 129.54, 121.52 (121.16), 119.96 (119.71), 117.04 (116.71), 47.90 (47.78), 46.29 (46.10), 31.05 (30.53), 28.02 (28.67), 23.37 (23.07), 15.22 (15.04), 14.87 (14.02, 14.21), 12.72 (12.67) ppm.

Example i-5 Synthesis of Precursor D-5

The procedures were performed in the same manner as described in the synthesis of the compound D-1 in Example i-1, excepting that the compound C-3 and tetrahydroquinaline were used rather than the compound C-1 and tetrahydroquinoline, to yield a precursor compound D-5. The yield was 48%.

In the ¹H NMR spectrum of the final product, a certain signal was split into a set of four signals at ratio of 1:1:1:1, resulting from the difficulty of rotating about the carbon-carbon bond (marked as a thick line in the Scheme 2) between phenylene and cyclopentadiene and isomerism pertaining to the existence of two chiral centers.

¹H NMR (C₆D₆): δ 7.32, 7.29, 7.22 and 7.18 (d, J=7.2 Hz, 1H), 6.96 (d, J=7.2 Hz, 1H), 6.84-6.68 (m, 1H), 6.60 (d, J=7.2 Hz, 1H), 4.00-3.92 (s, 1H, NH), 3.30-2.90 (m, 2H, NCHMe, CHMe), 2.90-2.55 (m, 2H, CH₂), 2.27 (s, 3H, CH₃), 1.94, 1.91 and 1.89 (s, 3H, CH₃), 1.65-1.54 (m, 1H, CH₂), 1.54-1.38 (m, 1H, CH₂), 1.23, 1.22, and 1.20 (s, 3H, CH₃), 1.00-0.75 (m, 3H, CH₃) ppm.

¹³C NMR (C₆D₆): 151.51, 145.80, 145.64, 145.45, 144.40, 144.22, 143.76, 143.03, 142.91, 139.78, 139.69, 139.52, 133.12, 132.74, 132.52, 132.11, 129.59, 121.52, 121.19, 120.75, 120.47, 119.87, 119.69, 116.99, 116.76, 47.90, 47.77, 46.43, 46.23, 32.55, 30.98, 30.51, 27.95, 27.67, 23.67, 23.31, 23.06, 16.52, 15.01, 14.44, 14.05 ppm.

(ii) Synthesis of Transition Metal Compound Example ii-1 Synthesis of Transition Metal Compound E-1

In a dry box, the compound D-1 (0.10 g, 0.36 mmol) synthesized in Example i-1 and dimethyl ether were put into a round-bottomed flask and cooled down to −30° C. N-butyl lithium (2.5 M hexane solution, 0.2 g, 0.71 mmol) was gradually added to the flask under agitation to activate the reaction at −30° C. for 2 hours. Warmed up to the room temperature, the flask was agitated for more 3 hours for the reaction. After cooled down back to −30° C., to the flask were added methyl lithium (1.6 M diethyl ether solution, 0.33 g, 0.71 mmol) and then TiCl₄.DME (DME: dimethoxyethane, 0.10 g, 0.36 mmol). The flask, while warmed up to the room temperature, was agitated for 3 hours and then removed of the solvent using a vacuum line. Pentane was used to extract the compound. The removal of the solvent produced 0.085 g of the final compound as a brownish powder (60% yield).

¹H NMR (C₆D₆): δ 7.09 (d, J=7.2 Hz, 1H), 6.91 (d, J=7.2 Hz, 1H), 6.81 (t, J=7.2 Hz, 1H), 6.74 (s, 2H), 4.55 (dt, J=14, 5.2 Hz, 1H, NCH₂), 4.38 (dt, J=14, 5.2 Hz, 1H, NCH₂), 2.50-2.30 (m, 2H, CH₂), 2.20 (s, 3H), 1.68 (s, 3H), 1.68 (quintet, J=5.2 Hz, CH₂), 0.72 (s, 3H, TiMe), 0.38 (s, 3H, TiMe) ppm.

¹³C{¹H} NMR (C₆D₆): 161.46, 142.43, 140.10, 133.03, 130.41, 129.78, 127.57, 127.34, 121.37, 120.54, 120.51, 120.34, 112.52, 58.50, 53.73, 49.11, 27.59, 23.27, 13.19, 13.14 ppm.

Example ii-2 Synthesis of Transition Metal Compound E-2

The procedures were performed in the same manner as described in the synthesis of the compound E-1 in Example ii-1, excepting that the compound D-2 was used rather than the compound D-1, to yield a transition metal compound E-2. The yield was 53%.

¹H NMR (C₆D₆): δ 7.10 (d, J=7.2 Hz, 1H), 6.91 (d, J=7.2 Hz, 1H), 6.81 (t, J=7.2 Hz, 1H), 4.58 (dt, J=14, 5.2 Hz, 1H, NCH₂), 4.42 (dt, J=14, 5.2 Hz, 1H, NCH₂), 2.50-2.38 (m, 2H, CH₂), 2.32 (s, 3H), 2.11 (s, 3H), 2.00 (s, 3H), 1.71 (s, 3H), 1.67 (quintet, J=5.2 Hz, CH₂), 0.72 (s, 3H, TiMe), 0.38 (s, 3H, TiMe) ppm.

¹³C{¹H} NMR(C₆D₆): 161.58, 141.36, 138.41, 137.20, 132.96, 129.70, 127.53, 127.39, 126.87, 121.48, 120.37, 120.30, 113.23, 56.50, 53.13, 49.03, 27.64, 23.34, 14.21, 13.40, 12.99, 12.94 ppm. Anal. Calc. (C₂₂H₂₇NSTi): C, 68.56; H, 7.06; N, 3.63. Found: C, 68.35H, 7.37 N, 3.34%.

Example ii-3 Synthesis of Transition Metal Compound E-3

The procedures were performed in the same manner as described in the synthesis of the compound E-1 in Example ii-1, excepting that the compound D-3 was used rather than the compound D-1, to yield a transition metal compound E-3. The yield was 51%. The final product was identified as a 1:1 mixture (the direction of the thiophene cyclic radical to the direction of the methyl radical on tetrahydroquinoline).

¹H NMR (C₆D₆): δ 7.11 and 7.08 (d, J=7.2 Hz, 1H), 6.96 and 6.95 (d, J=7.2 Hz, 1H), 6.82 and 6.81 (t, J=7.2 Hz, 1H), 6.77 and 6.76 (d, J=7.2 Hz, 1H), 6.74 and 6.73 (d, J=7.2 Hz, 1H), 5.42 (m, 1H, NCH), 2.75-2.60 (m, 1H, CH₂), 2.45-2.25 (m, 1H, CH₂), 2.24 and 2.18 (s, 3H), 1.73 and 1.63 (s, 3H), 1.85-1.50 (m, 2H, CH₂), 1.17 and 1.15 (d, J=4.8 Hz, 3H), 0.76 and 0.70 (s, 3H, TiMe), 0.42 and 0.32 (s, 3H, TiMe) ppm.

¹³C{¹H} NMR (C₆D₆): 159.58, 159.28, 141.88, 141.00, 139.63, 138.98, 134.45, 130.85, 130.50, 129.59, 129.50, 129.47, 127.23, 127.20, 127.17, 127.11, 120.77, 120.70, 120.40, 120.00, 119.96, 119.91, 118.76, 118.57, 113.90, 110.48, 59.61, 56.42, 55.75, 51.96, 50.11, 49.98, 27.41, 27.11, 21.89, 20.09, 19.67, 12.94, 12.91, 12.65 ppm.

Example ii-4 Synthesis of Transition Metal Compound E-4

The procedures were performed in the same manner as described in the synthesis of the compound E-1 in Example ii-1, excepting that the compound D-4 was used rather than the compound D-1, to yield a transition metal compound E-4. The yield was 57%. The final product was identified as a 1:1 mixture (the direction of the thiophene cyclic radical to the direction of the methyl radical on tetrahydroquinoline).

¹HNMR (C₆D₆): δ 7.12 and 7.10 (d, J=7.2 Hz, 1H), 6.96 and 6.94 (d, J=7.2 Hz, 1H), 6.82 and 6.81 (t, J=7.2 Hz, 1H), 5.45 (m, 1H, NCH), 2.75-2.60 (m, 1H, CH₂), 2.45-2.20 (m, 1H, CH₂), 2.34 and 2.30 (s, 3H), 2.10 (s, 3H), 1.97 (s, 3H), 1.75 and 1.66 (s, 3H), 1.85-1.50 (m, 2H, CH₂), 1.20 (d, J=6.8 Hz, 3H), 0.76 and 0.72 (s, 3H, TiMe), 0.44 and 0.35 (s, 3H, TiMe) ppm.

¹³C{¹H} NMR (C₆D₆): 160.13, 159.86, 141.33, 140.46, 138.39, 137.67, 136.74, 134.83, 131.48, 129.90, 129.78, 127.69, 127.65, 127.60, 127.45, 126.87, 126.81, 121.34, 121.23, 120.21, 120.15, 119.15, 118.93, 114.77, 111.60, 57.54, 55.55, 55.23, 51.73, 50.43, 50.36, 27.83, 27.67, 22.37, 22.31, 20.53, 20.26, 14.29, 13.51, 13.42, 13.06, 12.80 ppm.

Example ii-5 Synthesis of Transition Metal Compound E-5

The procedures were performed in the same manner as described in the synthesis of the compound E-1 in Example ii-1, excepting that the compound D-5 was used rather than the compound D-1, to yield a transition metal compound E-5. The yield was 57%. The final product was identified as a 1:1 mixture (the direction of the thiophene cyclic radical to the direction of the methyl radical on tetrahydroquinoline).

¹H NMR (C₆D₆): δ 7.12 and 7.09 (d, J=7.2 Hz, 1H), 6.96 and 6.94 (d, J=7.2 Hz, 1H), 6.82 and 6.80 (t, J=7.2 Hz, 1H), 6.47 and 6.46 (d, J=7.2 Hz, 1H), 6.45 and 6.44 (d, J=7.2 Hz, 1H), 5.44 (m, 1H, NCH), 2.76-2.60 (m, 1H, CH₂), 2.44-2.18 (m, 1H, CH₂), 2.28 and 2.22 (s, 3H), 2.09 (s, 3H), 1.74 and 1.65 (s, 3H), 1.88-1.48 (m, 2H, CH₂), 1.20 and 1.18 (d, J=7.2 Hz, 3H), 0.77 and 0.71 (s, 3H, TiMe), 0.49 and 0.40 (s, 3H, TiMe) ppm.

¹³C{¹H} NMR (C₆D₆): 159.83, 159.52, 145.93, 144.90, 140.78, 139.93, 139.21, 138.86, 135.26, 131.56, 129.69, 129.57, 127.50, 127.46, 127.38, 127.24, 121.29, 121.16, 120.05, 119.96, 118.90, 118.74, 117.99, 117.74, 113.87, 110.38, 57.91, 55.31, 54.87, 51.68, 50.27, 50.12, 34.77, 27.58, 27.27, 23.10, 22.05, 20.31, 19.90, 16.66, 14.70, 13.11, 12.98, 12.68 ppm.

Example ii-6 Synthesis of Transition Metal Compound E-6

The transition metal compound E-6 was synthesized according to the following Scheme 3.

Methyl lithium (1.63 g, 3.55 mmol, 1.6 M diethyl ether solution) was added dropwise to a diethyl ether solution (10 mL) containing the compound D-4 (0.58 g, 1.79 mmol). The solution was agitated overnight at the room temperature and cooled down to -30° C. Then, Ti(NMe₂)₂Cl₂ (0.37 g, 1.79 mmol) was added at once. After 3-hour agitation, the solution was removed of all the solvent with a vacuum pump. The solid thus obtained was dissolved in toluene (8 mL), and Me₂SiCl₂ (1.16 g, 8.96 mmol) was added to the solution. The solution was agitated at 80° C. for 3 days and removed of the solvent with a vacuum pump to obtain a reddish solid compound (0.59 g, 75% yield). The ¹H NMR spectrum showed the existence of two stereo-structural compounds at ratio of 2:1.

¹H NMR (C₆D₆): δ 7.10 (t, J=4.4 Hz, 1H), 6.90 (d, J=4.4 Hz, 2H), 5.27 and 5.22 (m, 1H, NCH), 2.54-2.38 (m, 1H, CH₂), 2.20-2.08 (m, 1H, CH₂), 2.36 and 2.35 (s, 3H), 2.05 and 2.03 (s, 3H), 1.94 and 1.93 (s, 3H), 1.89 and 1.84 (s, 3H), 1.72-1.58 (m, 2H, CH₂), 1.36-1.28 (m, 2H, CH₂), 1.17 and 1.14 (d, J=6.4, 3H, CH₃) ppm.

¹³C{¹H} NMR (C₆D₆): 162.78, 147.91, 142.45, 142.03, 136.91, 131.12, 130.70, 130.10, 128.90, 127.17, 123.39, 121.33, 119.87, 54.18, 26.48, 21.74, 17.28, 14.46, 14.28, 13.80, 13.27 ppm.

(iii) Preparation of Polypropylene

The individual polymerization reaction was carried out in an airtight autoclave using required amounts of a solvent, a co-catalyst compound, and monomers, and then a transition metal compound.

After completion of the polymerization, the polymer product was measured in regard to the molecular weight and the molecular weight distribution by the GPC (Gel Permeation Chromatography) (instrument: PL-GPC220 supplied by Agilent), and the melting point by the DSC (Differential Scanning calorimetry) (instrument: Q200 supplied by TA Instruments).

The isotacticity (Pentad, I.I, mmmm) of the polypropylene was analyzed by ¹³C NMR (Avance 400 Spectrometer supplied by Bruker) at 100° C. using the polypropylene product dissolved in trichlorobenzene and benzene-d₆ (C₆D₆). The measurement results are presented in Table 1.

Example iii-1

An autoclave (capacity: 2 L, stainless steel) was purged with nitrogen at the room temperature and filled with about 40 ml of a toluene solution (containing 10 wt. % of methylaluminoxane in toluene, 6 mmol of Al, as supplied by Albemarle). Then, 500 g of propylene was added, and the resultant solution was warmed up to 70° C. Subsequently, a solution (1.5 ml, 3.0 μmol of Ti) of the transition metal compound E-6 of Example ii-6 dissolved in toluene was added to the autoclave and then subjected to polymerization reaction for one hour.

After completion of the polymerization reaction, the resultant solution was cooled down to the room temperature and removed of the extra propylene. The polymer product thus obtained was collected and dried in a vacuum oven at 80° C. for at least 4 hours to yield polypropylene (137.9 g).

Example iii-2

An autoclave (capacity: 2 L, stainless steel) was purged with nitrogen at the room temperature and filled with 900 ml of n-hexane. Then, about 13.3 ml of a toluene solution (containing 10 wt. % of methylaluminoxane in toluene, 20 mmol of Al, as supplied by Albemarle) and 100 g of propylene were added in sequence. The resultant solution was warmed up to 70° C. Subsequently, a solution (5 ml, 10.0 μmol of Ti) of the transition metal compound E-6 of Example ii-6 dissolved in toluene was added to the autoclave and then subjected to polymerization reaction for one hour.

After completion of the polymerization reaction, the resultant solution was cooled down to the room temperature and removed of the extra propylene. The polymer product thus obtained was collected and dried in a vacuum oven at 80° C. for at least 4 hours to yield polypropylene (55.5 g).

Example iii-3

The procedures were performed in the same manner as described in Example iii-2, excepting that the polymerization reaction was carried out at 180° C. for 15 minutes to yield polypropylene (35.6 g).

Comparative Example iii-1

The procedures were performed in the same manner as described in Example iii-1, excepting that bisindenylzirconium dichloride (Ind₂ZrCl₂, supplied by Strem) was used as a catalyst rather than the transition metal compound E-6 of Example ii-6, to yield polypropylene (40 g).

Comparative Example iii-2

The procedures were performed in the same manner as described in Example iii-1, excepting that racemic ethylenebisindenylzirconium dichloride (supplied by Strem) was used as a catalyst rather than the transition metal compound E-6 of Example ii-6, to yield polypropylene (80 g).

TABLE 1 Comparative Comparative Example iii-1 Example iii-2 Example iii-3 Example iii-1 Example iii-2 Catalytic activity 46.0 5.55 14.2 13.3 26.7 (kg-pp)/(mmol-Ti)(hour) Mw (×10³) 349 186 102 5.2 30.3 Molecular weight 5.25 3.02 4.01 2.65 2.63 distribution (Mw/Mn) Melting point (° C.) N/A N/A N/A N/A 130.6 I.I. (%, mmmm) 9.6 7.7 6.4 7.2 78.2 Density (g/ml) 0.850 0.864 0.860 N.O. N.O. (Note: N.O. - Impossible to measure the property for the polymer with difficulty of preparing a press specimen due to the characteristic of the property.)

As can be seen from Table 1, a polypropylene with higher molecular weight and no melting point was obtained when polymerizing a propylene monomer using the catalyst of the present invention as in Examples iii-1, iii-2, and iii-3, rather than using the conventional transition metal compound as in Comparative Example iii-1 and iii-2. 

1. A method for preparing a polypropylene, comprising: polymerizing a propylene monomer in the presence of a catalyst comprising a transition metal compound represented by the following formula 1:

wherein M is a Group 4 transition metal; Q¹ and Q² are independently a halogen, C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl, C₆-C₂₀ aryl, C₁-C₂₀ alkyl C₆-C₂₀ aryl, C₆-C₂₀ aryl C₁-C₂₀ alkyl, C₁-C₂₀ alkylamido, C₆-C₂₀ arylamido, or C₁-C₂₀ alkylidene; R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, and R¹⁰ are independently hydrogen; C₁-C₂₀ alkyl with or without an acetal, ketal, or ether group; C₂-C₂₀ alkenyl with or without an acetal, ketal, or ether group; C₁-C₂₀ alkyl C₆-C₂₀ aryl with or without an acetal, ketal, or ether group; C₆-C₂₀ aryl C₁-C₂₀ alkyl with or without an acetal, ketal, or ether group; or C₁-C₂₀ silyl with or without an acetal, ketal, or ether group, wherein R¹ and R² can be linked to each other to form a ring; R³ and R⁴ can be linked to each other to form a ring; and at least two of R⁵ to R¹⁰ can be linked to each other to form a ring; and R¹¹, R¹², and R¹³ are independently hydrogen; C₁-C₂₀ alkyl with or without an acetal, ketal, or ether group; C₂-C₂₀ alkenyl with or without an acetal, ketal, or ether group; C₁-C₂₀ alkyl C₆-C₂₀ aryl with or without an acetal, ketal, or ether group; C₆-C₂₀ aryl C₁-C₂₀ alkyl with or without an acetal, ketal, or ether group; C₁-C₂₀ silyl with or without an acetal, ketal, or ether group; C₁-C₂₀ alkoxy; or C₆-C₂₀ aryloxy, wherein R¹¹ and R¹², or R¹² and R¹³ can be linked to each other to form a ring.
 2. The method as claimed in claim 1, wherein M is titanium (Ti), zirconium (Zr), or hafnium (Hf); Q¹ and Q² are independently methyl or chlorine; R¹, R², R³, R⁴, and R⁵ are independently hydrogen or methyl; and R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², and R¹³ are independently hydrogen.
 3. The method as claimed in claim 2, wherein at least one of R³ and R⁴ is methyl; and R⁵ is methyl.
 4. The method as claimed in claim 1, wherein the catalyst further comprises at least one co-catalyst compound selected from the group consisting of compounds represented by the following formula 6, 7, or 8: —[Al(R⁶¹)—O]_(a)—  [Formula 6] wherein R⁶¹ is independently a halogen radical, a C₁-C₂₀ hydrocarbyl radical, or a halogen-substituted C₁-C₂₀ hydrocarbyl radical; and a is an integer of 2 or above, D(R⁷¹)₃  [Formula 7] wherein D is aluminum (Al) or boron (B); and R⁷¹ is independently a halogen radical, a C₁-C₂₀ hydrocarbyl radical, or a halogen-substituted C₁-C₂₀ hydrocarbyl radical, [L-H]⁺[Z(A)₄]⁻ or [L]⁺[Z(A)₄]^(−[Formula) 8] wherein L is a neutral or cationic Lewis acid; Z is a Group 13 element; and A is independently a C₆-C₂₀ aryl or C₁-C₂₀ alkyl radical having at least one hydrogen atom substituted with a halogen radical, a C₁-C₂₀ hydrocarbyl radical, a C₁-C₂₀ alkoxy radical, or a C₆-C₂₀ aryloxy radical.
 5. The method as claimed in claim 4, wherein in the formula 6, R⁶¹ is methyl, ethyl, n-butyl, or isobutyl; in the formula 7, D is aluminum, and R⁷¹ is methyl or isobutyl; or D is boron, and R⁷¹ is pentafluorophenyl; and in the formula 8, [L-H]⁺ is a dimethylanilinium cation, [Z(A)₄]⁻ is [B(C₆F₅)₄]⁻, and [L]⁻ is [(C₆H₅)₃C]⁺.
 6. The method as claimed in claim 4, wherein the content of the co-catalyst compound is given such that the molar ratio of a metal in the co-catalyst compound with respect to one mole of a transition metal in the transition metal compound of the formula 1 is 1:1 to 1:100,000.
 7. The method as claimed in claim 1, wherein the catalyst comprises the transition metal compound of the formula 1 bound to at least one support selected from the group consisting of SiO₂, Al₂O₃, MgO, MgCl₂, CaCl₂, ZrO₂, TiO₂, B₂O₃, CaO, ZnO, BaO, ThO₂, SiO₂—Al₂O₃, SiO₂—MgO, SiO₂—TiO₂, SiO₂—V₂O₅, SiO₂—CrO₂O₃, SiO₂TiO₂—MgO, bauxite, zeolite, starch, and cyclodextrine.
 8. The method as claimed in claim 1, wherein the polymerization is carried out under conditions of −50 to 500° C. and 1 to 3,000 atm.
 9. The method as claimed in claim 1, wherein the polypropylene has a weight average molecular weight of 20,000 to 1,000,000; and a density of 0.8 to 0.9 g/ml.
 10. The method as claimed in claim 1, wherein the polypropylene has an isotacticity (Pentad I.I, mmmm) of 5 to 20%. 